Abstract
The rate constant of the reaction of methano- and cyclopentenofullerenes (С60R) with a peroxyl radical (PhCH(OO•)CH3) was measured in a model system of the radical-chain oxidation of ethylbenzene. Compounds with a succinimide dodecenoate substituent bonded with the fullerene molecule via the ‒С(О)(СН2)n– or –(СН2)n– groups (n = 1–5) were studied. The reactivity of С60R with respect to the ethylbenzene peroxyl radical was shown to increase relative to that of unsubstituted fullerene С60. Methanofullerenes were more reactive with the peroxyl radical than cyclopentenofullerenes. The rate constant of the reaction of С60R with PhCH(OO•)CH3 decreased when the number of methylene groups (n) increased. Quantum chemical modeling showed that the substituent atoms form hydrogen bonds with the peroxyl radical in the transition states of addition at the atoms of the fullerenyl moiety of methanofullerene that are nearest to the substituent. As a result, the energy barrier of the peroxyl radical addition to fullerene decreases. In the cases when succinimide dodecenoate lies far from the fullerene molecule, the reactivity of methano- and cyclopentenofullerenes with respect to the peroxyl radical decreases.
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This study was performed in accordance with the research plan at Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences (topic “Mechanism and kinetic laws of oxidative transformations involving highly active intermediates in chemical and biochemical processes,” FMRS-2022-0021, 122031400255-3).
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Translated by L. Smolina
Abbreviations and notation: F, degree of the inhibiting action of the inhibitor; ki, initiation rate constant; k1 and k2, rate constants of chain propagation; k6, rate constant of termination of the oxidation chain by recombination of peroxyl radicals; k7, inhibition rate constant; f, stoichiometric inhibition coefficient; PhCH2CH3, oxidized substrate (ethylbenzene); PhC•(H)CH3, PhCH(OO•)CH3, alkyl and peroxyl radicals formed from the substrate; AIBN, 2,2'-azo-bis-isobutyronitrile; EB, ethylbenzene.
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Yakupova, L.R., Diniakhmetova, D.R., Sakhautdinov, I.M. et al. Antioxidant Activity of Methano- and Cyclopentenofullerenes. Kinet Catal 63, 463–469 (2022). https://doi.org/10.1134/S0023158422050160
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DOI: https://doi.org/10.1134/S0023158422050160